Methods of in-field analysis

ABSTRACT

The present invention relates to the use of unique markers in the identification and tracking of objects. The present invention provides large numbers of unique markings for application to items as part of a marking system. The present invention provides a new approach to laboratory analysis and a means of rapid in-field identification of goods using a hand-held scanner. It provides data that can be used as a means of product tracking, identification of counterfeit product and to prove ownership of stolen goods.

RELATED APPLICATION(S)

This application is a continuation of U.S. application Ser. No.12/867,824, filed Aug. 16, 2010, which is the U.S. National Stage ofInternational Application No. PCT/GB2009/000225, filed on Jan. 26, 2009,published in English, which claims priority under 35 U.S.C. §119 or 365to Great Britain Application No. 0801479.7, filed on Jan. 26, 2008. Theentire teachings of the above applications are incorporated herein byreference.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing will be apparent from the following more particulardescription of example embodiments of the disclosure, as illustrated inthe accompanying drawings in which like reference characters refer tothe same parts throughout the different views. The drawings are notnecessarily to scale, emphasis instead being placed upon illustratingembodiments of the present disclosure.

A specific non-limiting embodiment of the invention will be described byway of example and with reference to the accompanying drawings in which:

FIG. 1 illustrates a side section of the illumination head used to focuson the item being analysed in accordance with the present invention; and

FIG. 2 shows a plan view from below of the illumination head shown inFIG. 1.

DETAILED DESCRIPTION

The present invention relates to the use of unique markers in theidentification and tracking of objects. The present invention provideslarge numbers of unique markings for application to items as part of amarking system. The present invention provides a new approach tolaboratory analysis and a means of rapid in-field identification ofgoods using a hand-held scanner. It provides data that can be used as ameans of product tracking, identification of counterfeit product and toprove ownership of stolen goods.

The cost of counterfeit goods to the world community is immense. Thepresent invention will help in the fight against counterfeit goods,which is a global market. Estimates vary, but this is generally acceptedas being 6% of world trade or equivalent to £260 bn.

The main tracking mechanism in use currently is radio frequencyidentification (RFID). However, RFID does suffer from limitations. Itcannot be covert, as although the chip is small, the antenna isgenerally big enough to be visible. It can be easily cloned bycounterfeiters. RFID also suffers from being absorbed by water andreflected by metal surfaces. RFID tracking systems are also plagued byprivacy/personal safety issues. Chip costs are also high.

Several systems are employed, or have been proposed in the patentliterature, which apply some optical determination method foranti-counterfeit or tracking purposes. Most widespread are the simpleUV- or IR-excited pigments formulated into inks and applied tobanknotes, passports, ID or other high-value documents. Such inks aredesigned to be visually assessed, are immediately apparent to anywould-be counterfeiter, easily replicated or even just imitated, sinceseveral substances would provide the same or very similar colours.Another one of their main weaknesses is the very limited number ofvisually distinguishable inks that can be produced, leading to the sameluminescent features being used in the same documents over long periods,leaving ample time to counterfeiters for perfecting their copies.

Other systems aim to exploit spectroscopic analysis of some appliedmarker. For example, US2002001080 and references therein describe theuse of absorption or reflectance spectroscopy, mainly applied to imagingof biological samples rather than security applications. WO2004114204and US20050017079 describe the use of a combination of luminescentquantum dots. WO2006086998 describes a system where the relativeintensity ratios in two luminescence bands are compared to one or morereference samples for validation, a system easily open to securitybreach if a counterfeiter were to be able to measure the referencesamples.

All of these systems still suffer from the same basic problem as thesimple visually-assessed luminescent inks, namely the limited number ofcombinations that are actually available to be used. Indeed, since allof the above systems rely on a limited set of data, from one or at mosttwo types of spectra, the number of individual markers that can bediscriminated in such systems is in the tens, hundreds or at mostthousands, and relies mostly on a limited number of compounds that canbe, therefore, identified and replicated by a skilled counterfeiter.

Another class of systems, exemplified by GB2319337 and by markerscontaining natural or synthetic DNA, require large-size, laboratorybased instrumentation to be analysed and specific procedures to collectand preserve the samples before any analytical result is available.Although the number of individual markers available can be, in suchcases, very large, indeed approaching the infinite, the lack of possiblein-field analysis is a serious obstacle for many applications.

The approach presented herein overcomes the limitations of all the typesof systems discussed.

The present invention relates to the use of unique markers in theidentification and tracking of objects. It provides large numbers ofunique markings for application to items as part of a marking system. Itprovides a new approach to laboratory analysis and a means of rapidin-field identification of goods using a hand-held scanner. It providesdata that can be used as a means of product tracking, identification ofcounterfeit product and to prove ownership of stolen goods.

According to the present invention there is provided a method ofsequentially collecting a plurality of spectral responses for analysingmixtures of materials, as claimed in claim 1 of the appended claims.

Also according to the present invention there is provided a method ofverifying the authenticity of an item, as claimed in claim 7 of theappended claims.

Further according to the present invention there is provided anapparatus for analysing mixtures of materials used as a uniqueidentifier, the mixtures of materials being applied to at least oneobject, as claimed in claim 12 of the appended claims.

Likewise according to the present invention there is provided ahand-held apparatus for remotely analysing mixtures of materials used asa unique identifier, the mixtures of materials being firstly applied toat least one item, as claimed in claim 21 of the appended claims.

It will be obvious to those skilled in the art that variations of thepresent invention are possible and it is intended that the presentinvention may be used, other than as specifically described herein.

The present invention provides a system for discriminating betweencounterfeit and genuine goods. It also provides a system for thetracking of manufactured goods both internally and after dispatch. Thesystem can also be used by law enforcement agencies as it provides acovert marking system that can be used to identify the ownership ofstolen goods, the premises from where they were stolen and any personnelpresent at the time of the offence.

The system is based on the tagging of items, directly as part of theitem, on the surface of the item, on a label on the item, as part, onthe surface or on a label on the primary (e.g., blister packs) orsecondary (e.g. box) packaging. Preferred options are those in which theitem itself is tagged. The most preferred option is the use of the tagas part of the item itself.

A wide range of tagging materials may be used including organics,inorganics, polymeric, molecular dyes or pigment, especially dopedpigments, for example pigments doped with rare earth elements, q-dots orother nanomaterials, including materials micro- or nano-encapsulated orcoated; delivered as paint or ink, in a film, incorporated in the bulkof the base material, for example as additives in polymeric and plasticmaterials, including polyolefin, polyesters and polycellulose, as alubricant or a wetting agent or otherwise present on the surface and inthe molecular-level surface roughness of the base material; tied to thebase material by chemical bonds or by physical attraction forces.

The skilled person will appreciate that the virtually infinite level ofcoding is a major feature of the invention. The complexity is producedthrough the combined sequential use of multiple spectral dimensions inrapid succession, with multiple analyses being undertaken in seconds.

Sequential analysis using different stimuli, such as short wave UV, longwave UV, visible and IR, coupled with time-based differentiation throughthe study of phosphorescent decay rates or time-resolved spectraprovides a multidimensional basis for the positive identification ofknown possible components in a mixture. This multi-dimensional spectralanalysis provides a quantity of data unachievable with any individualtechnique.

The skilled person will appreciate that the following different stimulicould be used:

-   -   emission energy in the short and long UV, visible and near IR        ranges, as a function also of stimulation energy    -   absorption/reflectance of incident radiation over the same        ranges    -   energy relationship between stimulation and signal as in Raman        spectroscopy    -   relationship between stimulation and emission versus time as in        phosphorescence spectroscopy

The same approach may be taken through sequential analysis byinstruments dedicated to each technique, although the time taken to doso and the ensuing costs argue strongly against this approach.

The present invention describes a scanner containing multiple differentsources within the one body, allowing different forms of spectralanalysis to be undertaken sequentially, being part of an overall systemfor generating mixtures; which provides a means of determining which ofa series of preset components are present in said mixtures; whichprovides data management and optional telemetry systems; which allowsrapid, possibly worldwide handling of data; and which providesinformation relevant to a wide range of applications.

When used as a method of identification applied to goods, the complexityof mixtures which can be produced approaches the infinite.

As an example of this approach, materials absorbing in the UV/visibleand IR regions of the spectrum can be physically mixed with and usedalongside materials emitting in various regions of the spectrum andthose with other varying spectral properties. If one were using asilicon detector covering 400 nm to 950 nm, then the spectral rangeavailable limits the number of materials which may be used to form acoding sequence

One embodiment would involve a detection element contained behind aseries of narrow bandwidth filters. The filters are set to maximisetransmission at the same wavelength as the maximum absorption/emissionfrom the absorber/emitter.

Alternatively, the filter may be moved across the detector and theabsorption/emission measured at each band-pass region to determine thosecomponents present. This may involve the use of a filter on a wheelwhich is spun in front of the detector and its position controlled andlogged via simple software.

A further embodiment would comprise the use of a miniature spectrometerable to resolve incident radiation and provide information on intensityversus wavelength.

A further embodiment would involve a lens system to focus photons ontothe detector cell of such a miniature spectrometer using free spaceoptics or through a length of optical fibre. This would provide a way ofmaximising the signal from a small, inaccessible, or uneven surface notsuitable for larger surface area detectors.

A further embodiment would provide a mechanism for simple unprocesseddata to be transmitted from the hand-held scanner to a central serverfor processing, with the result then being transmitted back to thescanner.

For example, when used in absorption mode the scanner would select thecorrect source from those available to irradiate the area underanalysis. Analysis of the reflected light would reveal the presence ofadditives through absorption of radiation at specific wavelengths. Thisanalysis would be conducted over the visible and near infra-red (NIR)regions of the spectrum.

A further embodiment would allow Raman spectroscopy to be carried outthrough the use of an appropriate illumination source and detectionrange.

The device can also be used to measure different forms of spectralemission resulting from different forms of stimulation. Infra red, longand short wave light sources can be selected as required to provideinformation on the presence or absence of anti-stokes materials,materials emitting in response to long wave UV, materials emitting inresponse to short wave UV and so on. The device can also pulse thesesources at preset time intervals so that phosphorescent materials withdifferent decay rates can also be used as part of the coding process.

Light sources can be LED's or other light-emitting devices such aslasers, arc lamps, OLED's, incandescent sources etc.

All measurements are conducted sequentially and not simultaneously. Thisallows repeated analysis of the surface, using different spectral rangesin both absorption and emission. Data from each scan is stored andprocessed separately. The data from the different spectral measurementsof each individual scan can be processed separately for simple cases;however, they are, in general, processed together in order to fullyexploit the information therein contained.

The sequential processing of the multiple spectra produced by theinvention may be used with various forms of spectral analysis including,but not limited to:

-   -   i) Visible absorption    -   ii) IR absorption    -   iii) Anti-stokes emissions    -   iv) Emissions with long wave UV stimulation    -   v) Emissions with short wave UV stimulation    -   vi) Emissions from phosphorescent materials under long wave UV        with slow phosphorescent decay rate    -   vii) Emissions from phosphorescent materials under long wave UV        with medium phosphorescent decay rate    -   viii) Emissions from phosphorescent materials under long wave UV        fast phosphorescent decay rate    -   ix) Emissions from phosphorescent materials under short wave UV        with slow phosphorescent decay rate    -   x) Emissions from phosphorescent materials under short wave UV        with medium phosphorescent decay rate    -   xi) Emissions from phosphorescent materials under short wave UV        with fast phosphorescent decay rate    -   xii) Raman spectroscopy

As an example, the above set of techniques would result in twelvedifferent data sets. Each data set will contain information indicatingthe presence or absence of various materials.

The in-field scanner can be made to different designs. One embodimentwould involve:

Illumination head

Spectrometer

Telemetry unit

Firmware

Power supply

Visual Display Unit

Whilst the skilled person can appreciate that many of the above aspectsof the system are known in isolation, the accumulation and use ofsequential analyses over different spectral and time domains asdescribed is particularly advantageous. When used in-field the separatedata sets may be collected and stored in separate buffers for subsequentanalysis at the central server. Once all the data sets have beencollected, they may then be transmitted to the central server, forexample via an encrypted mobile phone/Internet link. A typical completescan would take seconds to complete.

The combined sequential use of multiple spectral dimensions in rapidsuccession, with multiple analyses being undertaken in seconds isachieved through the illumination head and its connection to thespectrometer. When used to produce spectral emission the device has beendesigned to allow multiple excitation sources to focus on the area beinganalysed. An illumination head similar to that shown in FIGS. 1 and 2could be used. As depicted, the head is based upon the three lightsources (LS) above being focused onto the area being analysed (F). Asdiscussed previously, they could for example, be a long wave UV LED, ashort wave LED and an IR laser. Clearly both the UV LED's could be usedfor fluorescent and phosphorescent measurements. Assuming 3 differenttime delays for the phosphorescent measurements, this configurationalone could provide 9 different spectral ranges.

In the case of absorption/Raman analysis, interaction with the incidentradiation takes place and the light then reflected, elastically orin-elastically, from the surface is directed through the input optics(IO) to the end of the optical fibre connected to the spectrometer.

The signal from the illumination head then enters the spectrometer.Various configurations can be used in order to maximise the sensitivityand/or resolution of the device, including transmittance optics,reflective optics, holographic gratings or a combination of them.Detectors can be bi-dimensional CCD's, one-dimensional diode arrays orsingle-point photomultipliers. In one embodiment, multiple detectorssensitive in different spectral regions might be used. In a furtherembodiment, different light-dispersing elements might be employed fordifferent types of spectra.

With regard to the generation of mixtures, several options areavailable, that chosen depends upon which is best suited to the actualapplication. Assuming a qualitative argument initially, this can bebased on the premise that a component is either present or not, i.e.options/component. On this basis, the number of codes available is 2raised to the power given by the product of:

a) the number of components that can be discriminated in one data setand no other (even if their signal is present in several data sets), and

b) the number of data sets collected

For example 5 components separately detectable in each of 6 data setswill give a total number of codes equal to 230 or 109.

In a further embodiment, quantitative arguments may be used to furtherexpand the codes available. In order to obtain the complexity requiredin this case, the concentration of each of the components could forexample be increased stepwise by a power of 2. The concentration of eachof 4 components of a 5 component mixture, with the 5th being an internalstandard, would increase in steps, i.e. 1, 2, 4, 8. These primaryconcentration steps would then allow secondary concentrations to be usedto fill in the gaps in the concentration range. The secondaryconcentration steps serve as identifiers in terms of the combination ofprimary concentrations that have been used to produce the secondarylevel, as shown below:

Primary 1 2 4 8

The final concentrations are used as identifiers to determine which onesof the primary concentration steps are present, e.g.

Peak Height Relative to Internal Standard Components Present 0 0 1 1 2 23 1 + 2 4 4 5 1 + 4 6 2 + 4 7 1 + 2 + 4 8 8 9 1 + 8 10 2 + 8 11 1 + 2 +8 12 4 + 8 13 1 + 4 + 8 14 2 + 4 + 8 15 1 + 2 + 4 + 8

Giving total concentration ranges for each component of:

0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, i.e., 16concentration steps. Each primary concentration of a component is,effectively, a component in itself. Therefore, using 4 components, eachpossessing 4 primary concentration levels, affords 216 codes, or 65536codes available using just one data set. If using, as in the qualitativeexample, 6 data sets, the number of codes available, overall, would be2(16×6)=296, i.e. almost 8×1028. This embodiment allows a quantitativeapproach to be used to extend a qualitative argument by using secondaryconcentrations to indicate the presence or absence of each of theprimary levels.

In a further embodiment, a wider spectral range could be covered byusing a combination of detectors, for example, a silicon and an InGaAs.The device firmware would switch between detectors and combine theoutput from each to give a continuous spectrum covering a typical rangefor this combination of 400 to 1700 nm. A wider available spectral rangewould further increase the number of materials that could bediscriminated in each separate data set, increasing yet again, as aconsequence, the number of codes available.

This embodiment would increase the number of codes again, by an amountthat is dependent upon the number of materials. If one assumes 13components used in this range, with just 2 primary concentrations, i.e.4 concentration steps, and 6 types of measurement, the total number ofcodes would be almost 1047.

In a further embodiment, the system may be used with a hand-heldbattery-powered scanner capable of remote in-field operation. All thenecessary data handling can be provided by software residing on thescanner itself or on a separate local computer wired to the scanner orconnected to it by short-range wireless communication methods. In thisembodiment the system may be used typically to monitor and manage stockmovement from point of manufacture or to validate tickets used in accesscontrol.

A further, preferred embodiment would involve the scanner contacting acentral server from the field position as part of the field operation,via a suitable medium e.g. GPS, GPRS or satellite and transferring databack to the central server where the computations would be performed.The result of this analysis is then transmitted back to the fieldoperative, who will then respond in a prescribed manner.

The results from the server may also be forwarded to the customer. Thiswill allow the customer to update their own records in those areasimportant to them. The scanner location at the time of the measurementwill also be transmitted to the central server. This will allowcustomers to check the final location of goods, in terms of country,region, customer location, all of which helps the customer to identifyany potential diversion of their goods to unauthorised locations.

The response to the field operator may be as text, as symbols, as soundor vibration; the message can be of any level of detail, from a simple“yes/no” to a batch number or a description of the item, for a positiveresponse, and instructions on further action to take, for a negativeresponse; delivered to the in-field operator on the scanner itself viavoice or text mobile communication, satellite phone, area wi-fi orradio, or to another location and operator via any suitablecommunication method including, as before, voice or text mobilecommunication, satellite phone, area wi-fi or radio, and, additionally,e-mail, land-line phone, and access to a private web page.

In a further embodiment, the data may also be collected and stored onthe scanner for subsequent transmission when the scanner is in an areaof better reception, based upon whatever transmission methodology isbeing used.

The manner and extent in which the data is forwarded to the relevantcustomer, or handled by the customer can be customised to the requests,needs and procedures of each customer and specific application.

Various alterations and modifications may be made to the presentinvention without departing from the scope of the invention.

1. A method of analyzing mixtures of materials used as a uniqueidentifier, the method comprising: generating a mixture of one or morecomponents; applying the mixture on an object directly or as part of theobject, or on the surface of the object, or on a label on the object, oron a label on the primary or secondary packaging containing the object;and measuring the spectral emission and/or reflection and/or absorptionobtained from the object resulting from more than one form ofstimulation using an apparatus capable of producing more than one formof radiation, the data indicating the presence or not of the one or moreof the possible components of the mixture to determine the uniqueidentifier.
 2. The method of claim 1, further comprising the step of:illuminating a section of the object with one or more forms ofillumination.
 3. The method of claim 1 or claim 2, wherein the step ofgenerating a mixture additionally comprises providing the one or morecomponents at varying concentrations to determine the unique identifier.4. The method of claim 1, wherein the measurements are takensequentially by the apparatus.
 5. The method of claim 1, wherein the oneor more components are selected from the group consisting of: organics,inorganics, polymeric, molecular dyes or pigment, doped pigments,pigments doped with rare earth elements, q-dots or other nanomaterialsor combinations thereof.
 6. The method of claim 6, wherein the one ormore components are micro- or nano-encapsulated or coated on the object,or delivered as paint or ink, in a film, incorporated in the bulk of theobject, as additives in polymeric and plastic materials, includingpolyolefin, polyesters and polycellulose, as a lubricant or a wettingagent or otherwise present on the surface of the object and in themolecular-level surface roughness of the object; tied to the object bychemical bonds or by physical attraction forces or combinations thereof.7. The method of claim 1, wherein the step of measuring spectralemission and/or reflection and/or absorption obtained from the objectresulting from the forms of stimulation is selected from a groupconsisting of: visible absorption, IR absorption, anti-stokes emissions,emissions with long wave UV stimulation, emissions with short wave UVstimulation, emissions from phosphorescent materials under long wave UVwith slow phosphorescent decay rate, emissions from phosphorescentmaterials under long wave UV with medium phosphorescent decay rate,emissions from phosphorescent materials under long wave UV fastphosphorescent decay rate, emissions from phosphorescent materials undershort wave UV with slow phosphorescent decay rate, emissions fromphosphorescent materials under short wave UV with medium phosphorescentdecay rate, emissions from phosphorescent materials under short wave UVwith fast phosphorescent decay rate, Raman spectroscopy or combinationsthereof.
 8. The method of claim 2, wherein the step of illuminating asection of the object with forms of illumination is achieved using LED'sor other light-emitting devices such as lasers, arc lamps, OLED's,incandescent sources.
 9. The method of claim 1, further comprising thestep of: assigning a corresponding digital code stored in a database toeach generated mixture.
 10. A method of claim 10, further comprising thestep of comparing the data from measuring the spectral emission and/orreflection and/or absorption obtained from the object with thecorresponding digital code to verify the authenticity of the item. 11.The method of claim 11, wherein the step of comparing the data with thecorresponding digital code to verify the authenticity of the itemfurther comprises accessing the corresponding digital code stored on alocal or remote database.
 12. The method of claim 11, wherein the stepof comparing the data with the corresponding digital code to verify theauthenticity of the item further comprises accessing a remote databasefrom a remote position and receiving verification or otherwise via voiceor text mobile communication, satellite phone, area wi-fi, radio, e-mailor access to a private web page.
 13. The method of claim 10, wherein thestep of measuring the spectral emission and/or reflection and/orabsorption obtained from the object further comprises the step oflogging the time and location of the measurements and storing them on alocal or remote database.
 14. The method of claim 11, wherein theresults from the step of comparing the data with the correspondingdigital code to verify the authenticity of the item are held locally forsubsequent transmission.